1. Field of the Invention
The present invention relates to methods and compositions for stimulating production from subterranean formations by acid treating the formations.
2. Description of the Prior Art
Acid treatments of subterranean formations penetrated by well bores utilizing aqueous acid solutions have been carried out heretofore. Such treatments are commonly utilized in hydrocarbon containing subterranean formations to accomplish a number of purposes, the principal of which is to increase the production of hydrocarbons from the formations.
In treatments commonly referred to as "matrix acidizing", an aqueous acid solution is introduced into a subterranean formation under pressure so that the acid solution flows into the pore spaces of the formation. The acid solution reacts with carbonate rock and other reactive materials contained in the formation which increases the sizes of the pore spaces and increase the permeability of the formation. This in turn allows an increase in the flow of hydrocarbons through the formation into the well bore.
In treatments known as "fracture acidizing," a fracturing fluid is pumped into a subterranean formation under pressure and at a rate such that one or more fractures are produced. An acid solution is introduced into the fractures to etch flow channels in the fracture faces as well as to enlarge the pore spaces in the fracture faces. This in turn facilitates the flow of hydrocarbons through the subterranean formation into the well bore.
In both of the above-described acid treatments and in other similar treatments, the acid composition used can be combined with an inert gas, either in liquid or vapor form to "energize" the composition and facilitate its return from the treated formation.
It is highly advantageous for the aqueous acidizing solution utilized in subterranean formation acidizing procedures to be of relatively high viscosity whereby loss of the acid solution into highly permeable formations is minimized. The high viscosity also helps retard the reaction of the acid with reactive materials whereby the acid solution can be forced into areas of a subterranean formation remote from the well bore before the acid becomes spent. In addition, it is important that the spent acid solution retains enough viscosity to suspend fines and other solids generated by the acid reaction so that they are removed from the formation upon recovery of the spent acid solution.
While a variety of viscosity increasing agents have heretofore been utilized with aqueous acid solutions, e.g., hydratable polymers which are cross linked with suitable cross-linking agents, a problem which is often encountered is that the high viscosity aqueous acid solutions produced are not stable under conditions of use. For example, the effectiveness of a number of the viscosity increasing agents utilized heretofore rapidly decreases in the presence of acid whereby sufficient viscosity is not retained for the period of time required to carry out the desired treatment procedure.
By the present invention improved methods and high viscosity subterranean formation acid treating compositions are provided. The compositions have long-term stability, i.e., they retain sufficient viscosity over the times required for carrying out matrix acidizing and fracture acidizing procedures in subterranean formations whereby the spent compositions can suspend fines and other solids when removed from the formations.